Download Chapter 7:

Chapter 7:
Optical Properties of
Solids
Interaction of light with atoms
Insert Fig. 8.1
Allowed and forbidden electronic transitions
1
Insert Fig. 8.3 or equivalent
Ti3+ absorption:
eg
← t2g
2
Ruby Laser
Al2O3 corundum
Free ion
term
4F
4F
Octahedral
Field
4T
1
Ruby Laser
intersystem
crossing
4T
2
Insert Fig. 8.4
nonradiative
transition
2E
4F
4A
2
Initial excitations are spin allowed:
t2g2eg1  t2g3
 4A1g and 4T1g  4A1g
4T
2g
Red emission at 694 nm
2E
 4A1g
t2g3  t2g3
3
Describing electrons in multi-electron systems: L and ML
Orbital angular momentum 

l (l  1)
Orbital angular
momentum has
ml = 2
magnitude and
2l+1 spatial
orientations with
ml = 1
respect to the z axis
(i.e. the number of
ml = 0
values of ml),
vectorial summation
of the individual l
ml = -1
values is necessary
 2h
+2(h/2)
+(h/2)

6 (h / 2 )
6 (h / 2 )
0
6 (h / 2 )
-(h/2)
ml = -2
Orbital angular momentum 
M L   ml
-2(h/2)

6 (h / 2 )
6 (h / 2 )
h
L( L  1)
2
Describing electrons in multi-electron systems: S and MS
The spin quantum number, s, determines the magnitude of the spin
angular momentum of an electron and has a value of ½.
For a 1 electron species, ms is the magnetic spin angular
momentum and has a value of +½ or -½.
Spin angularmomentum

S (S  1)
 2h
for a multi-electron system
M S   ms
For a system with n electrons, each having s = ½, possible values of S (always
positive) fall into two series depending on the total number of electrons:
•S = 1/2, 3/2, 5/2, ….
for an odd number of electrons.
•S = 0, 1, 2, ….
for an even number of electrons.
For each value of S, there are (2S + 1) values of MS:
MS: S, (S-1), …-(S-1), -S
4
Microstates and term symbols
Microstates – the electronic states that are possible for a given electronic configuration.
•no two electrons may have the same set of quantum numbers (Pauli exclusion principle)
•only unique microstates may be included
ns2 configuration
Cannot physically distinguish between the electrons, so must use sets of
quantum numbers to decide if the microstates (rows in the table) are the same or
different.
First microstate: l = 0, ml = 0, ms = +1/2; l = 0, ml = 0, ms = -1/2
Second microstate: l = 0, ml = 0, ms = -1/2; l = 0, ml = 0, ms = +1/2
Term Symbol
Multiplicity of the term
( 2 S 1)
L
{
L=0
L=1
L=2
L=3
L=4
S term
P term
D term
F term
G term
Describing electrons in multi-electron systems: J and MJ
Total angularmomentum

J ( J  1)
 2h
Total angular momentum quantum number J takes values:
(L + S), (L + S -1), …., |L-S|, and these values can be 0,1,2 … or 1/2, 3/2, 5/2, ….
(2S+1) possible values of J for S < L, and (2L+1) possible values of J for L < S.
The value of MJ denotes the component of the total angular momentum along the z
axis.
Allowed values of MJ: J, J-1, …, -(J-1), -J.
The method of obtaining J from L and S is based on LS (or Russell –Saunders)
coupling, aka spin-orbit coupling.
Full Term Symbol
{
Multiplicity of the term
( 2 S 1)
J value
LJ
L=0
L=1
L=2
L=3
L=4
S term
P term
D term
F term
G term
5
Consider a free d3 ion
ml
+2
+1
0
-1
-2
How many ways can the electrons be located in the d-orbitals?
Number of microstates 
{2(2l  1)}!
10! 10 * 9 * 8


 120
x!{2(2l  1)  x}! 3!*7!
3!
What are the values for ML and MS for the following configurations?
ML
MS
3
3/2
5
1/2
Designation
+++
(2,1,0)
+-+
(2,2,1)
Organize each of the microstates and group by ML and MS values:
MS
ML
3/2
1/2
5
4
3
2
1
0
Note the symmetry of the configurations if the spins of all the electrons are reversed
6
Construct a microstates number table from the previous table
MS
ML
3/2
1/2
-1/2
-3/2
5
4
3
2
1
0
-1
-2
-3
-4
-5
By examination of the previous we determine there are groups of
microstates described by specific terms.
22 microstates spanning ML = 5 to -5; MS = +1/2 to -1/2.
18 microstates spanning ML = 4 to -4; MS = +1/2 to -1/2.
28 microstates spanning ML = 3 to -3; MS = +3/2 to -3/2.
14 microstates spanning ML = 3 to -3; MS = +1/2 to -1/2.
2×10 microstates spanning ML = 2 to -2; MS = +1/2 to -1/2.
12 microstates spanning ML = 1 to -1; MS = +3/2 to -3/2.
6 microstates spanning ML = 1 to -1; MS = +1/2 to -1/2.
2H
2G
4F
2F
2D
4P
(two)
2P
22+18+28+14+2*10+12+6 = 120 microstates
Using Hund’s rules, predict the ground state term:
1) Term with the higher spin multiplicity has lower energy
2) If two or more terms have the same multiplicity, the term having the
highest value of L has the lowest energy
3) For terms having the same multiplicity and L, the level with the lowest
value of J is the lower in energy if the sublevel is less than half filled,
and the level with the highest value of J is the more stable if the sublevel is more than half-filled. (if half filled, L is zero and J=S)
The ground state of a free d3 ion is the 4F term.
7
4F, 4P,2H,2G,2F,2D,2D,2P
These are the terms for a free ion, but the terms splits into
components in an octahedral field
Term
Components in octahedral field
S
A1g
P
T1g
D
T2g + Eg
F
A2g + T2g + T1g
G
A1g + Eg + T2g + T1g
H
Eg + T1g + T1g +T2g
I
A1g + A2g + Eg + T1g + T2g + T2g
Tanabe-Sugano
diagram for a d3
ion
8
Light Amplification by Stimulated Emission of Radiation (LASER)
• Q switch (like mirror) on one end switches from reflective to
transmitting the light and a pulse of light emitted
• Population inversion is created, decay from excited state takes
place more slowly than expected for spontaneous emission.
• Allows pumping of excess of electrons into excited state
• Electrons in excited state are stimulated to decay by an
incident photon of same energy.
• Cascade effect, generate an intense beam of monochromatic
radiation, in-phase and coherent.
Crystals used as lasers
Ion
Host
Ti3+
Λ (nm)
Sapphire (Al2O3)
650-1100 (tunable)
Nd3+
Fluorite (CaF2)
1046
Sm3+
Fluorite
708.5
Ho3+
Fluorite
2090
Nd3+
CaWO4
1060
Nd3+
YVO4
1064
Nd3+
Y3Al5O12 (YAG)
Nd/YAG laser
1064
A green laser (typically) is composed of Nd3+ in YVO4
which emits photons with wavelength 1064 nm, which
are frequency doubled to 532 nm by a non-linear
optical second harmonic generation material KTP,
potassium titanyl phosphate (KTiOPO4) crystal.
9
Laser systems
Type
Medium
λ (nm)
Avg. Output
Mode
Gas
He-Ne
633
0.1-50 mw
cw
Ar
488, 514
5 mW-20 mW
cw
Ruby (Cr:Al2O3)
694
30 mJ-100 J
pulse
Nd:YAG
1064
10 mJ-100 J
pulse
Solid State
Semiconductor
Excimer
Dye tunable
GaAlAs
750-905
1-40 mW
cw
GaN
405
5 mW
cw
AlGaInP, AlGaAs
630-900
5 mW
cw
ArF
193
50 W
pulse
XeF
351
30 W
pulse
300-1000
2-50 W
cw or pulse
Lasers have different modes: continuous wave (cw) or pulsed.
Phosphors in Fluorescent Lights
http://home.howstuffworks.com/fluorescent-lamp.htm
Phosphors: solids that absorb
energy and re-emit it as light
10
Spectrum of a “Blacklight”
SrB4O7F: Eu2+ phosphor
Phosphor Material Composition
Alkaline earth halophosphates: 3Ca3(PO4)2∙CaF2 doped with Sb3+ and Mn2+
11
Phosphor Material Composition
•Tb3+, Ce3+:LaPO4
or
Tb3+:CeMgAl11O19
for green and blue.
•Eu:Y2O3 for red
Upconversion
Atomic states of Ho3+
12
Emission spectrum of hydrogen
Absorption spectrum of GaAs
Linear chain of s orbitals
Linear chain of p orbitals
13
Infinite 1D Chain of H atoms
c0
c1
c2
c3
c4
k=/a
E(k)
k=/2a
EF
0
k
/a
k=0
a
k=0  orbital phase does not change when we translate by a
k=π/a  orbital phase reverses when we translate by a
Band Structure: Linear Chain of F (no mixing)
Antibonding 2pz s*
Doubly degenerate
EF
Antibonding 2px/2py *
Doubly degenerate
Antibonding 2s s*
Bonding 2px/2py 
Bonding 2pz s
Bonding 2s s
0
k
/a
14
Energy Bands
Band structure of copper
15
Energy bands near the junction in a p-n junction
neutral p-type
- - - - - -
+ +
+
+
++ +
+ + +
+ + +
+ + +
+
+
neutral n-type
depletion region
Gallium arsenide laser
16
Quantum Wells – blue lasers
17
Refractive Indices
Values of Refractive index
Water 1.33
Normal glass/acrylic plastic 1.5
Polycarbonate 1.56
Highest optical plastic 1.66
Bismuth glass >2
Diamond 2.42
Calcite (CaCO3)
• Exhibits birefringence, since
it has different
polarizabilities in directions
of different crystal axes,
hence different refractive
indices for light polarized
perpendicular to these axes.
• The unique axis is the optical
axis.
• When light is passed through
the material, it splits into
two beams travelling at
different speeds due to
different refractive indices.
• Birefringence can only occur
for crystals displaying
asymmetry.
• Between 190 and 1700 nm, the
ordinary refractive index for calcite
varies roughly between 1.6 and 1.4,
while the extraordinary refractive
index varies between 1.9 and 1.5.
• Ordinary rays polarized in plane
perpendicular to optical axis,
extraordinary rays polarized in the
plane parallel to the optical axis.
18
Cloak of Invisibility
• Uses birefringence in crystals of calcite, with the optical
axes of each are at 30° to the interface
• The path of light is shown by the blue trace.
• The ray exits in the direction it would have if reflected off the surface in
the absence of the object and the cloak, as shown by the dashed trace.
Cloak of Invisibility
Demonstration of a macroscopic volumetric cloaking device operating at
visible frequencies, which can conceal objects of sizes of at least 3
orders of magnitude larger than the wavelength of light in all three
dimensions, and works for a specific polarization of the incident light.
19
Optical Fibers
Optical fibers are used to transmit light in the way metal wires
transmit electricity
•optical communications, data transmitted to intensity, time between
pulses and length of a pulse.
•signal must be maintained so that a detectable signal still exists at
other end of the cable (sometimes km) effort spent at reducing energy
loss in commercial optical fibers
•laser beam diverges less than conventional light.
•fibers usually constructed with variable refractive index and light is
sent down the central core, which is surrounded by a material with a
lower refractive index.
•Light deviating from a straight path is totally internally reflected
and hence remains in the core.
Ex
Direction of Propagation
k
x
z
z
y
By
An electromagnetic wave is a travelling wave which has time
varying electric and magnetic fields which are perpendicular to each
other and the direction of propagation, z.
Traveling wave along Z
20
Rayleigh Scattering
Intensity I of light scattered by
a single particle from a beam of
unpolarized light of wavelength
λ and intensity I0 is given by:
where R is the distance to
the particle, θ is the
scattering angle, n is the
refractive index of the
particle, and d is the
diameter of the particle.
21
•The light travelling
through can interfere
destructively with
reflected light.
Photonic Crystals
•Reflected waves are all
in phase with one
another and out of
phase with the incident
light , destructive
interference occurs.
opal
Metamaterials
Unusual optical, electric and magnetic properties, including a
negative refractive index.
• Doppler effect reversed (radiation travelling towards observer is
shifted to longer wavelengths, red shifted)
22
Cloaking
Coordinate Transformation
Cancellation of scattering
23